Membrane Technology for Treatment of Process Affected Waters CONRAD – Oils Sands Process Water Workshop Membrane Technology for Treatment of Process Affected Waters Hadi Husain and Steve Kroll ZENON Environmental Inc., Canada

Ultrafiltration has come of age for Industrial and Municipal Water and Wastewater Treatment This has resulted from progressive improvements in permeability, and reduction in production cost. ZENON is focused on use of membranes for water and wastewater treatment We have played a key role in this transformation through invention and evolution of our ZeeWeed® immersed membranes and the ZenoGem® bioreactor Largest ZeeWeed® water filtration plant, when fully operational, will produce in 75,000 m3/d water Largest industrial recycle plant produces 26,000 m3/d tertiary water for RO at a Mexican refinery Largest ZenoGem® plant treats up to 19,000 m3/d Very high level of reliability has been achieved, with most plants designed for a 24h/d, 365 d/y basis.

MF/UF Membranes in Water Treatment Complex system Membranes in pressure vessels High operating pressure High cross-flow velocity High flux Small/expensive module Low permeability membrane Inherited features from RO and older UF technologies Simple system Shell-less membranes Low operating pressure Direct (dead-end) filtration Air to enhance solids removal Moderate flux Large/low cost module High permeability membrane Current trend

ZeeWeed® Operation Permeate Pump Raw Water Treated Water Reject Air

Evolution of ZeeWeed® Membranes Superficial Loading 0.0 2.0 4.0 6.0 8.0 10.0 12.0 Filtration rate (gal/min/ft2) ZW-150 (1995) ZW-500a (1997) ZW-500b (1999) ZW-1000 (2000) Typical range for rapid sand filtration Evolution of ZeeWeed® Membranes Development started in 1991 First applied to difficult wastewater treatment (landfill leachates). Developed product and processes for simpler applications 4 generations of backward compatible products Energy consumption

ZeeWeed® for Water Filtration Cost

ZeeWeed® Water Filtration Capacity Year * As of March 30, 2000 (000’s m3/day) 122% Annual Growth

Wastewater: Energy Consumption

Wastewater: Cost

ZenoGem® - Biological Wastewater Installed Capacity (m3/day)

ZeeWeed® Based Plants are Highly Reliable We have developed strong fibres with high permeability. This, combined with operation under low delta p and mild aeration enhances reliability, reduces energy use and increases membrane life For direct filtration of low solids water, low delta p operation permits the use of unsupported, small, low cost hollow fibres Inner support material and the outer polymer coating imparts high strength, toughness and durability to the hollow fibre product used for high solids application Immersed membrane configuration, combined with innovative module designs and aeration techniques result in stable operation in high solids environment

The ZeeWeed® Membrane Supported hollow fibre with outside-in flow (0.9 mm ID, 1.9 mm OD) Chlorine-resistant polymeric membrane Pore size of 0.04 µm nominal in the ultrafiltration range Permeate drawn by suction on the permeate side Air bubbling induces turbulence to keep membrane clean

ZeeWeed® Applications - Membrane Bioreactor (ZenoGem®) for wastewater treatment - Direct filtration (surface water, well water, secondary effluent, process water ) - Filtration coupled with coagulation/ oxidation/ powdered activated carbon

ZeeWeed® ZenoGem® Operation Membranes contained in frames within aeration tanks Operating vacuum -1 to -8 psi (greater vacuum = greater flow) Vacuum created by conventional ANSI end suction pump Pumping rate controlled by VFD based on aeration tank level Membrane scouring provided by airflow (100 SCFM / ZW-500c cassette) (4 psi at base of cassette) Membrane air provides 50% of biological requirements Fine bubble aeration supplements membrane aeration Fully automated backpulse (20 seconds every 15 minutes)

ZenoGem® for Water Reuse RO Pre-treatment in Florida Location: Florida Keys Municipality required very high effluent quality, at all times to: Protect marine life Irrigate golf course What was considered: Activated sludge SBR ZenoGem®

Reverse Osmosis Pre-Treatment Removal of suspended solids larger than 0.035 microns and fouling organic molecules Typical advantages of ultrafiltration for RO pre-treatment: Absolute filter at 0.035 - 0.1 micron Lower chemical consumption - no need to settle the coagulated organics Lower sludge volume to be disposed Easy to operate Produces a high quality water (SDI < 3), allowing for easy operation of RO Plant (ie: lower power requirement, longer cleaning intervals, longer membrane life)

Florida WTP - RO Feed - 3,500 m3/day 5,5,3,1

ZenoGem® for TN Removal with Pre-Denitrification RQ Q Q(1+R) Anoxic Aerobic D.O. > 1 mg/L NH4+ NO3- NO3-  N2 D.O. < 0.5 mg/L Effluent [TN] = [TKNox] / (1+R) + TKNeff TN < 10 mg/L R > 4 TN < 6 mg/L R > 8 TN < 3 mg/L R > 20 Assume TKNox = 40 mg/L TKNeff = 1 mg/L

Influent Wastewater

Process Optimization Nitrogen Removal

Florida WW Plant RO Conductivity Removal Efficiency

Full-Scale Industrial Applications of ZeeWeed® for Water Filtration Direct filtration of surface water for process use Tertiary filtration of wastewater effluents for water reuse Pre-treatment of industrial or municipal effluent for process use or for boiler make up water prior to reverse osmosis Coagulation coupled with filtration for TOC and colour removal for direct process use or as a pretreatment to RO Oxidation coupled with filtration for iron, manganese, arsenic and other heavy metals removal

Treatment Options Option 1 Option 2 Option 3 UF UF PRE-TREATMENT UF PAC Option 3

ZeeWeed® for Filtration Applications Coagulation coupled with filtration for TOC and colour removal

What is UF Enhanced Coagulation ? Coagulation of dissolved organics at a higher coagulant dosage than required for turbidity removal Acid/caustic addition may be utilized for pH adjustment (pH ~ 6.0 - 6.2) Advantages of the ZeeWeed® Enhanced Coagulation Process: - TOC removal - up to 75% - colour removal - up to 95% - SDI of 2 or less - less chemical usage and less sludge for disposal

Enhanced Coagulation Coagulant Permeate Pump Flash Mixer Feed Water High solids concentatration in tank Flocculation Chamber Bleed/Concentrate Air

ZW Pretreatment for Boiler Water RO Feed in a Northern Alberta Application (Ferric chloride dosage: 50-60 mg/l)

ZeeWeed® / Powdered Activated Carbon (PAC) Activated carbon is used to ZW tank to adsorb organic impurities. Dosage rates and retention time of activated carbon in ZeeWeed tank is managed to provide the best conditions for removal of a specific contaminant, and its adsorption rates on carbon ZW has a high tolerance for solids. Systems operate at up to 30 g/l of suspended solids. Aeration provides mixing. We have found that permeability can actually improve with the addition of activated carbon

MIB Removal Figure 1A: MIB removal with 50 mg/l PAC using ZW10 module 37 71 179 212 5 7 10 50 100 150 200 250 1 2 3 4 MIB (ug/l) Feed Permeate

ZeeWeed® for Filtration Applications Tertiary filtration of secondary effluents for water reuse

Sludge dewatering / disposal Evolution of Water Reclamation Treatment Train at Orange County Water District Original Pre- treatment Primary clarifier Activated sludge Secondary clarifier Lime softening Air stripping Recarbo- nation Sand filtration GAC adsorption Clarification RO Raw sewage Treated water Sludge dewatering / disposal Sludge digester With MF/UF pre-treatment to RO Pre- treatment Primary clarifier Activated sludge Secondary clarifier MF/UF RO Raw sewage Treated water Sludge dewatering / disposal Sludge digester

Case Study: Poland Secondary Effluent Reuse Pretreatment of municipal secondary effluent RO to industrial cooling circuit feedwater Operating since September 1999 Plant Capacity: 5,400 m3/d Permeate SDI < 2

ZeeWeed®/RO Pilot Program for Process Affected Waters ZeeWeed offers the following advantages for water recycle at SCL: 0.04 micron ultrafiltration Consistent, high quality effluent with significant reduction of RO biofouling High recovery Low SDI, leading to improved RO operation High MLSS loading in bioreactor leading to superior nitrification Pilot program focusing on three ZeeWeed® configurations: Physical chemical treatment for O&G and suspended solids Physical chemical with PAC addition to the ZeeWeed tank to further enhance O&G removal ZenoGem® with nitrification for ammonia and toxicity reduction Reverse Osmosis for TDS reduction to be piloted with each of the above

Pilot Program Targets and Schedule SDI of 2 or less ZeeWeed system recovery of >90% RO recovery >80% Ammonia less than 1 mg/l in biological nitrification ZW permeate turbidity of less than 0.1 NTU RO salt rejection of >99% Total program duration of six months starting today

Conclusions The ZeeWeed technology is highly suited to RO pretreatment for recycle of SCL’s process affected water streams It provides 0.04 micron barrier to suspended matter, and combined with physical chemical or biological processes, can remove a wide variety of contaminants effectively and consistently Low pressure operation, low energy use, and high recovery potential make this technology particularly suitable for this application Pilot program is underway to apply ZW-RO, in combination with physical – chemical and biological pretreatment for recycle of process affected waters for boiler water make-up and other potential reuse applictions